CN102745674A - Manufacturing mold and manufacturing method of flake graphite film - Google Patents
Manufacturing mold and manufacturing method of flake graphite film Download PDFInfo
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- CN102745674A CN102745674A CN2012102104222A CN201210210422A CN102745674A CN 102745674 A CN102745674 A CN 102745674A CN 2012102104222 A CN2012102104222 A CN 2012102104222A CN 201210210422 A CN201210210422 A CN 201210210422A CN 102745674 A CN102745674 A CN 102745674A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 116
- 239000010439 graphite Substances 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 112
- 238000000034 method Methods 0.000 claims abstract description 108
- 238000003763 carbonization Methods 0.000 claims abstract description 56
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
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- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 63
- 238000003475 lamination Methods 0.000 claims description 48
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- 238000000465 moulding Methods 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000012528 membrane Substances 0.000 claims description 33
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000004642 Polyimide Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000004575 stone Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
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Abstract
The invention relates to a manufacturing mold and a manufacturing method of a flake graphite film, and the method comprises the following steps: selecting a biaxially-oriented polyimide film as a raw material film, setting a manufacturing mold, placing the cut raw material film into the mold in a spaced and laminated manner, pressing the raw material film, performing a carbonization procedure in a carbide furnace, cooling, adjusting the pressure applied to the raw material film, performing a graphitization procedure, naturally cooling to obtain the finished product graphite film. The invention provides a complete and particular manufacturing process suitable for batch production of flake graphite films with high thermal conductivity, can realize batch production of artificial graphite films with high quality; the graphite film has good heat diffusivity and strong bending resistance, and is suitable for the solution of the heating problem for miniature electronic product components.
Description
Technical field
The present invention relates to a kind of mfg. moulding die and method of manufacture of the graphite film as heat sink material, relate to a kind of mfg. moulding die and method of manufacture of flaky graphite film especially.
Background technology
Along with the continual renovation of electronic product is regenerated, develop to thinner, lighter direction day by day, the heating problem of its electronic devices and components is also more and more outstanding.Traditional utilize metal fin, tinsel are carried out the method for heat conduction and heat radiation, and utilize the method for fan forced heat radiation more and more can't satisfy the change request that electronic product makes rapid progress.
Utilize metal fin to dispel the heat, exist shortcomings such as taking the electronic product internal space is big, increase electronic product quality to electronic product.Use tinsel (like Copper Foil, aluminium foil or other metallic substance etc.) heat radiation separately, then the work-ing life of electronic devices and components or speed of response can reduce; Because the not high (copper that is used for the electronic component heat radiation of the thermal conductivity of metallic substance itself; Be that radiating effect is best in the metal, its thermal conductivity is about 400W/mK, and thermal conductivity is meant under the steady heat transfer condition; The temperature difference of the both side surface of 1 meter thick material is 1 degree; The heat that in 1 second, transmits through 1 square metre of area), the heat that can leave is less, and it is not enough that the relative high electronic devices and components of thermal value simply utilize the tinsel heat radiation; Its thermal equilibrium temperature that reaches at last can surpass the normal use temperature of electronic devices and components, causes electronic devices and components shorter work-ing life.Be directed to the big electronic devices and components of thermal value, such as the cpu of computer etc., its radiating mode often adopts metal fin collocation fan to dispel the heat.But there is following shortcoming in fan heat radiation: the one, and the easy dust suction of fan along with the increase of working hour of fan, is understood residual a certain amount of dust on fan and electronic devices and components, and overstocked dust can affect greatly the radiating rate of electronic devices and components; The 2nd, noise is bigger, even so-called quiet fan also can't avoid a certain amount of noise to exist fully now; The 3rd, it is bigger to take up room, and along with the market requirement of the light-dutyer more thinning of electronic product, the use volume of fan is to there is certain obstruction.
Carbon is a kind of very magical element.The material that the occurring in nature thermal conductivity is the highest is exactly carbon simple substance a---diamond, and its thermal conductivity is 2300W/mK.The allotropic substance of carbon---graphite has the high conductivity properties that compares favourably with diamond.Usually the graphite-structure material as heat conduction, heat radiation has graphite block, graphite flake (common graphite block, graphite flake thickness are between 0.3mm to 3mm), expandable graphite sheet (claiming the natural stone ink film again) and rostone ink film.
Graphite block and graphite flake mainly are used for the preparing various kinds high-temperature resistant container, perhaps as the heating pipeline, and the pad of hot-fluid pipeline etc., also use as heat sink material gradually in recent years.Such as, high-power LED lamp is with regard to the method for useful graphite flake heat conduction, and the heat conductive silica gel, the high hot silicone grease that replace in the past serve as the use of heat conduction pad.In addition, matrix materials such as the ceramic graphite of graphite-containing composition, plastics graphite, the alternative metals section bar uses as radiating equipment, but many-sided defective such as its snappiness is poor, is existing to bend, and is frangible.
Natural stone ink film (expandable graphite sheet) is to utilize natural graphite powder or graphite scale to handle through acidic solution, and interpolation tackiness agent etc. are in the moulding of certain temperature condition pressed.The thermal conductivity of natural stone ink film is the highest at present can only reach 500W/mK, generally has only 300 to 400 W/mK.The thermal conductivity of natural stone ink film is suitable with the copper of present stage, and the electronic product that generally can only be confined to dispel the heat less demanding uses.
The rostone ink film is meant the graphite film that utilizes carbonaceous polymeric membrane to make through carbonization, graphitization technique.The basic characteristics of rostone ink film are: thin, the thinlyyest can accomplish 10 microns, generally all below 100 microns; Thermal conductivity high (thermodiffusion performance in other words is good, thermal diffusivity high); Good heat conductivity; The thermal conductivity of its in-plane is generally more than 800 W/mK; Manufacture craft is good, and the plane thermal conductivity of the rostone ink film of degree of graphitization more than 90% can reach 1500 to 1800 W/mK, and perfectly the thermal conductivity of the in-plane of rostone ink film can reach 2400W/mK in theory; Snappiness is good, and anti-bending performance is splendid; Conductivity is strong.The purposes of rostone ink film very extensively can be applied to multiple fields such as electronics, space flight, military project.Be specially adapted to solve the heating problem of small-sized electronic product heating components and parts,, can reach the ideal radiating effect, and be suitable for very convenient such as the cpu that is directed against electronic products such as smart mobile phone, notebook computer, panel computer, navigating instrument, battery etc.Apply processing through superfusion, can directly be attached on the heating components and parts of electronic product, solve its heating problem.The rostone ink film will be made crucial contribution for above-mentioned electronic product develops towards thinner, lighter, integrated direction.
Japan is in relatively leading status at research, the production field of rostone ink film at present.More domestic research mechanisms, institutes etc. rostone ink film that begins one's study from the early 1980s has also been obtained pleasurable achievement so far.But; The all unexposed complete synthetic graphite film production method of numerous synthetic graphite film production patents and document; Like publication number is the patent of invention of CN101687647A; Disclose the invention of a kind of " graphite film and graphite composite film ", making and the greying that its content is mainly set forth selection, the polyimide of the preparation bending resistance folding endurance synthetic graphite film contents such as the scope and the way of heating of exerting pressure are not told about its concrete manufacture craft.Publication number is that the patent of invention of CN1826288A discloses a kind of " film like graphite and method of manufacture thereof " for another example; What its content was mainly set forth is the manufacturing as synthetic graphite pleurodiaphragmatic in terspace material film polyimide for people's likewise known, the concrete technology of openly not making graphite film.The domestic literature of Zhang Peng, Chi Weidong, Shen Cengmin " high temperature cabonization is to polyimide (PI) membrane structure and Effect on Performance " for another example; Do not set forth the manufacture craft of graphite film yet, just told about the change procedure of raw material in carbonization, greying engineering with and the variation of physicochemical property.The method of manufacture that Chinese patent document CN102149633A (application number is 2009801359470) discloses a kind of carbonaceous film reaches by its graphite film that makes; It discloses a kind of method of manufacture of growing the graphite film of size, web form; This method of manufacture is in the carbonization process of making processes, to lean on the frictional force that produces between the raw material film to keep the integrity of film; Thereby the graphite film of make making not fold, do not produce ripple; But the graphite film that this method is made is not owing to give the planarization that certain pressure is prone to guarantee surface reorganization in its decomposition course in the process of making; Therefore the heat conductivility of the actual graphite film of processing is insuperior, and its crystal structure of graphite is flourishing inadequately, even the later stage can not change the defective that this making method is brought through rolling processing.
The all unexposed complete synthetic graphite film production method of not only numerous synthetic graphite film production patents and document, and the concrete making method of rostone ink film itself has diversified characteristics, is not limited to a kind of mode.
Summary of the invention
The technical problem that the present invention will solve provides a kind of mfg. moulding die and concrete method of manufacture complete, that be fit to produce in batches flaky high thermal conductivity graphite film.
Realize that the technical scheme of first purpose of the present invention provides a kind of mfg. moulding die of flake graphite film, comprises base, column, loam cake, barrier sheet and heatproof weight.Column has 4.
Base is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, and diameter is 20 to 50cm.The front, rear, left and right portion of base respectively is provided with the through hole of 1 upward and downward, and the adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base, and the axis of 4 through holes be positioned at the concentric cylindrical side of base on, 4 through holes are equipped with IT.
4 root posts are processed by graphite, and it is cylindric that column is, and the diameter of the through hole on its diameter and the base is corresponding, and the bottom of every root post is provided with the outside screw that the IT with the through hole of base is complementary.4 root posts are screwed in corresponding 1 through hole of base by its threaded portion, lower end respectively from top to bottom, thereby make 4 root posts be fixed on the base, thereby obtain down membrane module.
Barrier sheet has a rectangular shape, the imaginary foursquare length of side that its side ratio 4 root posts are surrounded little by 0% to 0.2%.Barrier sheet is processed by high temperature material.Barrier sheet is horizontally set on when using in the space that base and 4 root posts surround.
The heatproof weight is processed by high temperature material.The shape of heatproof weight is consistent or slightly little with the shape of barrier sheet, and lower surface is smooth.The heatproof weight is horizontally set on when using in the space that base and 4 root posts surround.
The shape of loam cake and size are identical with base, and loam cake is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, the equal diameters of diameter and base.The front, rear, left and right portion of loam cake respectively is provided with the through hole of 1 upward and downward, and the adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base, and the axis of 4 through holes be positioned at the concentric cylindrical side of loam cake on, 4 through holes of loam cake are unthreaded hole.Pass a corresponding root post respectively from top to bottom by its 4 through holes when loam cake uses, and be fixed on the top of 4 root posts.
The preferred graphite flake of the manufactured materials of barrier sheet, rostone ink film or natural stone ink film, more preferably natural stone ink film.
The preferred carbon element class of the manufactured materials of heatproof weight material, more preferably graphite block.The heatproof weight is a bottom shape and barrier sheet rectangular-shaped weight of a size.
Realize that the technical scheme of second purpose of the present invention provides a kind of method of manufacture of flake graphite film, comprises the steps:
1. choose starting material, choose diaxial orientation, double refractive inde greater than 0.1, Young's modulus is greater than 400kgf/mm
2, the polyimide film of tensile strength more than 50Mpa be as the raw material film.
2. mfg. moulding die is set, and above-mentioned mfg. moulding die adopts the mfg. moulding die of above-mentioned flake graphite film.
3. the raw material film that 1. step is obtained is cut into the shape that is suitable for being placed in the mfg. moulding die that 2. step obtain.The foursquare shape size that is surrounded according to 4 root posts of mfg. moulding die; The polyimide film that 1. step is obtained is cut into corresponding square shape and obtains the raw material film, and the length of side of the foursquare barrier sheet of side ratio of the raw material film of the complete every square shape of cutting is little by 0.5% to 1%.
4. the raw material film that 3. step is obtained and the spacing piece 4 of respective numbers are placed in the following membrane module that 2. step obtain with the mode of interval lamination; Be specially first raw material film of the smooth placement of upper surface of the base of the following membrane module that 2. obtains in step; First barrier sheet of overlapping placement on first raw material film then; Second raw material film of overlapping again placement; Second barrier sheet of overlapping placement on second raw material film then, so superimposed until all raw material films and barrier sheet all are placed in the mfg. moulding die with space eclipsed mode, thus obtain the subassembly of interval lamination and counterdie.The process of the above-mentioned overlapping placement in space abbreviates lamination process at interval as, and the overlapping placement in space then abbreviates lamination at interval as.
5. the raw material film in the interval lamination that 4. step is obtained and the subassembly of counterdie is exerted pressure; The heatproof weight is placed on the upper surface of the barrier sheet that is positioned at the top of interval lamination that 4. step obtain and die assembly, thereby obtains the interval lamination of weight application and the parts of mould.The pressure range of exerting pressure is 3 to 10g/cm
2The interval lamination of the weight application that 6. 5. step is obtained and the parts of mould are put into the inner chamber of carbide furnace.
The inner chamber of the carbide furnace of the interval lamination of having put into weight application that 7. 6. obtains in step and the parts of mould, the inner chamber to carbide furnace vacuumizes earlier, charges into nitrogen or rare gas element again and forms inert environments.
8. under the inert environments that 7. step obtains; With the carbonization temperature of the raw material film of the parts of the interval lamination of carbide furnace heat temperature raising to weight application and mould and begin carbonization; And under the highest carbonization temperature, be incubated 30 to 120 minutes and completion carbonization, naturally cooling then.The highest carbonization temperature that is provided with in the insulation is at 1000 ℃ to 1400 ℃.
The adjustment of exerting pressure of raw material film after the carbonization of the interval lamination of the weight application that 9. 8. step is obtained and the parts of mould; Open the bell of carbide furnace; Replacement heatproof weight above the parts of the interval of weight application lamination and mould, the pressure range of exerting pressure are 5.0 to 100g/cm
2
10. the carbide furnace that 9. step is obtained being provided with the parts of interval lamination and mould after adjustment is exerted pressure forms inert environments again.Earlier with vacuumizing in the stove, applying argon gas or helium to normal pressure, pressure-fired or little negative pressure then.
After
waits for the carbide furnace naturally cooling, take out mfg. moulding die and obtain the finished product graphite film.
Step specified operational procedure 7. is: earlier carbide furnace is vacuumized, fill with rare gas element to normal pressure such as nitrogen or argon gas or pressure-fired, little negative pressure then.And then vacuumize again, fill with rare gas element to normal pressures such as nitrogen or argon gas or pressure-fired, little negative pressure again.
The rare gas element nitrogen, the preferred little negative pressure of pressure condition.
Step 1. in, the preferred all benzene type acid dianhydrides of polyimide raw material film and p-phenyl's diamines are as the prepared polyimide film of the polymer raw of polyimide.
Step 8. in, the temperature-rise period when above-mentioned carbonization begins is included in 500 ℃ to 700 ℃ especially 550 ℃ to 650 ℃ the time, keeps slowly heating up with the speed below the 5 ℃/min.
In step carbonization process 8., in the time of 500 ℃ to 700 ℃, taked the operation of further decompression, the warm area air pressure that makes carbide furnace is little negative pressure-0.1KPa to-0.01KPa, after 700 ℃, keeps atmospheric pressure state.
In the step
, heating schedule is warming up to top temperature in the graphitization process with the speed of 10 ℃ of-50 ℃/min in the above-mentioned graphitization process.
After 4. step is accomplished, before 5. step carry out; Loam cake is arranged on the subassembly that 4. step obtain at interval lamination and counterdie; Loam cake is enclosed within respectively on the position, upper end of corresponding 1 root post by its 4 through holes from top to bottom; Lower surface until loam cake contacts with the upper surface that is in uppermost barrier sheet, thus make step 5. and heatproof weight 9. be placed on the upper surface of loam cake.
The present invention has positive effect: mfg. moulding die of (1) flake graphite film of the present invention and method of manufacture provide a kind of concrete ME complete, that be fit to produce in batches flaky high thermal conductivity graphite film; Can produce high-quality rostone ink film in batches; This graphite film thermal diffusivity is good, the bending resistance folding endurance is strong, is suitable for solving small-sized electronic product components and parts heating problem.
(2) mfg. moulding die of flake graphite film of the present invention and method of manufacture have adopted the method that the raw material film is suitably exerted pressure in carbonization, graphited process; Fully guaranteed the planarization of produced graphite film and the prosperity of graphite crystallization structure, so its thermal diffusivity is more superior.
(3) mfg. moulding die of flake graphite film of the present invention and the method for manufacture temperature of carbide furnace in graphitizing process is controlled at more than 2800 ℃, has guaranteed graphited adequacy.
(4) mfg. moulding die of flake graphite film of the present invention and method of manufacture are taked slowly to heat up in 500 to 700 ℃ temperature-rise period of carbonization process and are made the raw material film guarantee flaw not occur in violent the decomposition in the process of recombinating as far as possible, and reactions.
(5) mfg. moulding die of flake graphite film of the present invention and method of manufacture can be taked constant temperature measures in carbonization process, with guarantee the raw material film in certain specific warm spot reactions, fully, thereby make the graphite film of desired characteristic.
Description of drawings
Fig. 1 is the structural representation of the mould in the embodiments of the invention 1;
Fig. 2 is the upward view of Fig. 1.
Mark in the above-mentioned accompanying drawing is following: base 1, column 2, loam cake 3, barrier sheet 4, heatproof weight 5, raw material film 6.
Embodiment
(mfg. moulding die of embodiment 1, flake graphite film)
See Fig. 1, the mfg. moulding die of present embodiment comprises base 1, column 2, loam cake 3, barrier sheet 4 and heatproof weight 5.Column 2 has 4.
See Fig. 1 and Fig. 2, base 1 is a graphite block that is round pie, and its thickness is 1 to 3 centimetre (present embodiment is 2 centimetres), and diameter is 30cm.The front, rear, left and right portion of base 1 respectively is provided with the through hole of 1 upward and downward; The adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base 1; And the axis of 4 through holes be positioned at base 1 a concentric cylindrical side on, 4 through holes are equipped with IT.
4 root posts 2 are processed by graphite, and column 2 is cylindric, and the diameter of the through hole on its diameter and the base 1 is corresponding, and the bottom of every root post 2 is provided with the outside screw that the IT with the through hole of base 1 is complementary.4 root posts 2 are screwed in corresponding 1 through hole of base 1 by its threaded portion, lower end respectively from top to bottom, thereby make 4 root posts 2 be fixed on the base 1, thereby obtain down membrane module.
The shape of loam cake 3 and size are identical with base 1, and loam cake 3 is graphite blocks that are round pie, and its thickness is 1 to 3 centimetre (present embodiment is 2 centimetres), and diameter is 30cm.The front, rear, left and right portion of loam cake 3 respectively is provided with the through hole of 1 upward and downward; The adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base 1; And the axis of 4 through holes be positioned at loam cake 3 concentric cylindrical sides on, 4 through holes of loam cake 3 are unthreaded hole.
Barrier sheet 4 has a rectangular shape, the imaginary foursquare length of side that its side ratio 4 root posts 2 are surrounded little by 0% to 0.2%.Various types of materials more than the top temperature that barrier sheet 4 employing fusing points are set in carbonation process is processed preferred graphite flake, rostone ink film or natural stone ink film, more preferably natural stone ink film.Because the thickness of graphite flake is more than 0.3mm, and more crisp, it is cracked to add after exerting pressure that the high temperature expansion capacity is prone to, and thickeies that then occupation space can be big, influence volume production; The rostone ink film is then relatively more expensive, and soft, the easy breakage of matter; So barrier sheet 4 selects the natural stone ink film to process the best, the thickness of natural stone ink film is at 0.1mm to 0.5mm, and the natural stone ink film of this thickness has had certain rigidity, easy lamination.The size of the barrier sheet of present embodiment is 21cm*21cm, and thickness is 0.2mm, adopts the natural graphite coiled material to cut and processes.
(method of manufacture of embodiment 2, flake graphite film)
The method of manufacture of the flake graphite film of present embodiment comprises following several steps:
1. choose starting material.
Can be a kind of in polyimide (PI), polyoxadiazole (POD), polyamide (PA), polybenzoxazole (PBO), polyphenyl and two oxazoles (PBBO), polybenzothiozole (PBT), polyphenyl and double thiazole (PBBT), polybenzimidazole (PBI), polyphenyl and the two imidazoles high-temperature resistant aromatic property polymeric membranes such as (PBBI) generally as the polymeric membrane raw material of preparation graphite film.Wherein (PI) is more preferably polyimide with polyoxadiazole (POD) is preferred raw material to polyimide.Because acid dianhydride and diamines as the raw material of synthesis of polyimides have variety.The polymeric membrane raw material of the manufacturing flake graphite film that the present invention adopts is exactly a polyimide.
The polyimide material that the present invention adopts requires the molecular orientation property of its in-plane good; The carbonization more easily of such polyimide material, greying; The orientation of graphite crystallization also can improve, and the graphite film bending resistance folding endurance that makes is good, thermal conductivity is high (thermal diffusivity is high), the isotropy degree on surface is high.
In-plane molecular orientation property is meant that the molecule segment of polymeric membrane is abreast to same direction arrangement.The in-plane of the polymeric membrane molecule segment of not oriented is arranged and vertical direction (thickness direction) is arranged all free arrangement in polymerization process, by intermolecular interaction force decision.Do not having under the external force function influence, intermolecular interaction force is identical, so physics, the chemical property of all directions of the polymeric membrane molecule segment of not oriented (comprising in-plane and vertical direction) are same sex character.But the isotropy of this polymeric membrane molecule segment is not to be the isotropy that is fit to make graphite film, and just molecule segment is arranged the same sex of generation under equimolecular power interacts.Making good graphite film must make polymeric membrane make its molecule segment have orientation at in-plane under external force.
Applying the aligned of external force has two kinds, and a kind of is uniaxial orientation, and another kind is a diaxial orientation.Uniaxial orientation is meant that a direction at polymeric membrane applies pulling force, thereby makes polymeric membrane to extended by force direction.As in the length direction unilateral stretching, then the length of film can increase, and thickness and width dwindle, and then the molecule segment of length direction has had orientation.Diaxial orientation is meant that external force is at two orthogonal direction stretching polymeric membranes; Be length direction and width two-way stretch; The length of the polymeric membrane of diaxial orientation and width all can increase; Its thickness reduces, and the molecule segment of polymeric membrane is arranged with respect to the stretching plane parallel, and the molecule segment of stretching plane inboard (can be considered thickness direction) is a random alignment.It is thus clear that the polymeric membrane of diaxial orientation has the horizontal direction isotropic nature in the stretching plane, out-of-plane other directions that stretch are different in nature character with respect to the stretching plane then.Therefore, utilize the in-plane and the vertical direction of the rostone ink film that polymeric membrane makes also to exist anisotropy.
The polyimide film of diaxial orientation is exactly the raw material polymeric membrane that present embodiment is selected for use.There is orientation that orientation degree is just arranged; Orientation degree is high more, orientation is good more the easier carbonization of polyimide raw material film, greying; The quality of the graphite film that can make (thermal diffusivity, electroconductibility etc.) is high more: the raw material film is through behind the diaxial orientation; The molecule segment of stretching face is arranged in parallel and more helps the transmission of intermolecular heat, and heat loses littler in intermolecular transmittance process, and efficient is better; Simultaneously molecular chain receives to make behind the force-extension intermolecular reactive force itself to reduce, and its molecular breakdown is reset energy needed and just reduced relatively like this, so carbonization easily, greying.
The orientation degree of confirming Kapton has a lot of methods, as: wide-angle x-ray diffraction, double refraction method, sound wave propagate method, infrared dichroism method etc.Its stretching in-plane of Kapton and the physical properties of thickness direction that these methods all are based on after the orientation are anisotropy.Confirm that with the double refraction method raw material film orientation degree is an example: double refractive inde is the refractive index (establishing Nx representes) of expression raw material membrane plane direction and vertically poor perpendicular to the refractive index (establishing Nz representes) of the thickness direction of membrane plane, i.e. Δ n=Nx-Nz.The big more expression raw material of Δ n value film orientation degree is good more, and the material Δ n that selects for use as present embodiment answers ﹥ 0.10.Nx should many values, promptly in a plurality of angles of raw material membrane plane (like 0 ° of direction, 30 ° of directions, 45 ° of directions etc.) value, use a plurality of Nx that obtained to subtract Nz, get its MV and are regarded as Δ n more accurately.Nz also can many values, but the difference of Nz is very little, are because operation or instrument cause minute differences, so can suitably lack value sometimes.Another purpose of the many values of Nx can judge whether the raw material film belongs to diaxial orientation.For example; The refractive index of representing 0 ° of direction (can in membrane plane, freely confirm) with Nx1; Represent in the membrane plane refractive index value with 0 ° of vertical 90 ° of direction of direction with Nx2; Approach zero or equal zero then that illustrative material is a diaxial orientation like the value of Nx1-Nx2, otherwise explain that then the raw material film is a uniaxial orientation, the present embodiment preferable material is the polyimide of diaxial orientation.
Tensile strength also can be regarded as the index that raw material film orientation degree is judged, tensile strength is high more, and raw material film orientation degree is good more; The judge index of more direct raw material film orientation degree is exactly a tensile strength, and tensile strength is big more, and orientation degree will be high more.But the prerequisite of these two indexs is raw material films is diaxial orientations.
The Young's modulus of raw material film is high more in addition, and the graphite film quality that makes is also good more, and its Young's modulus of polyimide raw material film that present embodiment adopts should be greater than 400kgf/mm
2(every square millimeter of kgf refers to apply on every square millimeter the area pressure of 1 kgf).Can come the Young's modulus of raw material film is detected through LaWave Young's modulus detector.More be prone to make the polyimide raw material film of desired properties as the preferred all benzene type acid dianhydrides of the polymer raw of polyimide and p-phenyl's diamines.
The model that present embodiment adopts Liyang Huajing Electronic Material Co., Ltd. to produce be the H type, length is that 10 meters, width are 500 millimeters, the coiled material type polyimide film of 25 microns of thickness, tensile strength 50MPa, the diaxial orientation starting material as the raw material film.
2. mfg. moulding die is set.The mfg. moulding die of the flake graphite film that employing is obtained by embodiment 1.
3. the polyimide film that 1. step is obtained is cut into the shape that is suitable for being placed in the mould.
The foursquare shape size that is surrounded according to 4 root posts 2 of mfg. moulding die; The polyimide film that 1. step is obtained is cut into corresponding square shape and obtains raw material film 6, and the length of side of the foursquare barrier sheet 4 of side ratio of the raw material film 6 of the complete every square shape of cutting is little by 0.5% to 1%.The size of every tablet raw material film is set to be slightly less than the maximum sized reason that can place in the mfg. moulding die be that the raw material film can produce and expands in the carbonization course of processing; If the size of raw material film is the same with the overall dimension that mfg. moulding die can be placed; The raw material film can be wiped with the edge of mfg. moulding die because of expansion in the course of processing mutually so; Thereby cause carbonization good raw material membrane portions edge curvature, fold or breakage; In the greying course of processing, must not repair equally, influence the overall quality of graphite film.The size of every tablet raw material film of present embodiment is the square shape of 20.8cm*20.8cm, totally 200.
4. the raw material film 6 that 3. step is obtained is placed in the following membrane module that 2. step obtain with the mode of interval lamination, obtains the subassembly of lamination and counterdie at interval.
See Fig. 1; First raw material film 6 of the smooth placement of upper surface of the base 1 of the following membrane module that 2. obtains in step; First barrier sheet 4 of overlapping placement on first raw material film 6 then, second raw material film 6 of overlapping again placement, second barrier sheet 4 of overlapping placement on second raw material film 6 then; So superimposed until all 200 raw material films 6 all are placed in the mfg. moulding die with space eclipsed mode with barrier sheet 4, thus the subassembly of lamination and counterdie at interval obtained.
The process of the above-mentioned overlapping placement in space abbreviates lamination process at interval as, and the overlapping placement in space then abbreviates lamination at interval as.At interval should keep the smooth of raw material film 6 in the lamination process as far as possible, and aiming between raw material film 6 and the barrier sheet 4.
Being used for barrier sheet 4 at interval, the reason of lamination is to prevent that raw material film 6 is welded together in the following process process.
5. loam cake 3 is arranged on the subassembly that 4. step obtain at interval lamination and counterdie; Loam cake 3 is enclosed within respectively on the position, upper end of corresponding 1 root post 2 by its 4 through holes from top to bottom; Lower surface until loam cake 3 contacts with the upper surface that is in uppermost barrier sheet 4, thereby obtains the parts of interval lamination and mould.
6. interval lamination that 5. step is obtained and the raw material film 6 in the die assembly are exerted pressure.Heatproof weight 5 is placed on the upper surface of loam cake 3 of interval lamination that 5. step obtain and die assembly, thereby obtains the interval lamination of weight application and the parts of mould.
The raw material film 6 of the gravity of heatproof weight 5 after through 3 pairs of laminations of loam cake applies certain pressure so that carry out carbonization process.
Exert pressure is for planarization that guarantees raw material film 6 in the carbonization process and the graphite film that makes required quality.In the carbonization process, raw material film 6 molecules can decompose and carry out molecular recombination, if inappropriate exerting pressure, the raw material film 6 of carbonization can produce flaws such as ripple.In carbonization process, when decomposing, raw material film 6 produces contraction by a relatively large margin at its in-plane, if pressure is excessive, hinder its contraction, raw material film 6 will crack, perhaps fracture of hole.Molecular breakdown can produce tar in the carbonization process in addition, if the excessive discharge that is unfavorable for tar of pressure is residual even decompression also has minute quantity tar, thereby influences the quality of graphite film.The pressure range that carbonization process is exerted pressure is 3 to 10g/cm
2(restraining every square centimeter).In addition, exerting pressure also is evenly to have created condition for the good raw material film 6 of carbonization in the graphite-like structure growth of its in-plane, helps greying.The quality settings of heatproof weight 5 is 2000g in this step.
The interval lamination of the weight application that 7. 6. step is obtained and the parts of mould are put into the inner chamber of carbide furnace.The high temperature cabonization equipment that present embodiment adopts Changsha promise atmospheric electricity scarabaeidae skill ltd to produce.
The inner chamber of the carbide furnace of the interval lamination of having put into weight application that 8. 7. obtains in step and the parts of mould forms inert environments.Earlier the inner chamber to carbide furnace vacuumizes, and charges into nitrogen or rare gas element again and forms inert environments.The purpose that forms inert environments is not contaminated for the center warm area of protecting carbide furnace, prolongs service life of equipment, also is to prevent that airborne gas from high temperature reacting with raw material film 6 simultaneously.Raw material film 6 can not carry out carbonization under the natural air atmosphere.Specified operational procedure is: earlier carbide furnace is vacuumized; Fill with rare gas element to normal pressures such as nitrogen or argon gas or pressure-fired, little negative pressure then, said pressure-fired is meant that the environmental stress of surveying is higher than the gaseous tension state of normal pressure (i.e. normal atmosphere) 1 to 400Pa; Said little negative pressure is meant that the environmental stress of surveying is lower than the gaseous tension state of normal pressure (i.e. normal atmosphere) 1 to 400Pa, and for example the normal atmosphere in external environment is under the situation of 1Mpa, and the absolute pressure value of little negative pressure-0.1KPa is 99.9KPa; Can vacuumize again this moment, and the air that not have during previous like this vacuumizing to discharge further obtains diluting to be taken away, and then fill with rare gas element to normal pressure such as nitrogen or argon gas or pressure-fired, little negative pressure.Rare gas element is preferably both economical, and the inertia degree is inferior to the nitrogen of argon gas and helium.Generally before heating schedule begins, vacuumize, the operation of inflated with nitrogen or rare gas element; Though before the raw material decomposition temperature, there is not the selection of atmosphere; In case but heating schedule starts; Follow-uply be difficult to control the operation that vacuumizes with inflated with nitrogen or rare gas element, and airborne impurity also might contaminated feedstock before raw material film 6 decomposition temperatures, thus be chosen in vacuumize before heating schedule starts, the operation of inflated with nitrogen or rare gas element.
Formed inert environments in the present embodiment is for being full of nitrogen.Carbide furnace keeps the condition atmospheric condition of normal pressure, pressure-fired or little negative pressure to finish until carbonization, is cooled to normal temperature, and perhaps the blow-on temperature blow-on below 300 ℃ all is fine; Little negative pressure is the pressure condition of comparative optimization, produces because in raw material film 6 carbonization processs, have tar, and little negative pressure relatively is fit to tar exhausting, the protection body of heater and the stove heart.
9. under the inert environments that 8. step obtains, the carbonization temperature of the raw material film 6 of the parts of the interval lamination of carbide furnace heat temperature raising to weight application and mould is begun carbonization, insulation about 30 minutes under carbonization temperature and accomplish carbonization.The highest carbonization temperature that is provided with in the insulation is at 1000 ℃ to 1400 ℃, and general 1000 ℃ get final product, and preferred 1200 ℃, more preferably 1400 ℃.More than 1000 ℃, the carbonization of raw material film 6 is meant after the molecular breakdown of raw material film 6 goes out carbon and recombinates, basically forms the hexagonal carbon stratum reticulare face of graphite-like structure, and be that the graphited operation of carrying out next step has been created condition.The pyritous reason that 1200 ℃ or 1400 ℃ for example are set more than 1000 ℃ is to make 6 carbonizations of raw material film more abundant, and content is higher in the graphite film of carbon after molecular recombination, and graphite-like structure generates Du Genggao, and degree of graphitization is also just higher.
Temperature-rise period when described carbonization begins is included in 500 ℃ to 700 ℃ especially 550 ℃ to 650 ℃ the time, keeps slowly heating up with the speed below the 5 ℃/min, and all the other temperature sections can be according to the requirement design of technology separately.Also can design the homothermic time period in the carbonization.The purpose that the constant temperature time section is set be for guarantee as far as possible raw material film 6 at one time, decompose under the same temperature and reassemble into the reaction of charcoal solid, like this material breakdown recombinate more even; If keep persistently overheating; Because the temperature of each point of device interior warm area is actual and inhomogeneous at one time; Cause that raw material film 6 is actual at one time can not to decompose recombining reaction accordingly under identical temperature; The level of response of natural raw material film 6 each points is also just different, and the possibility that has flaw is just arranged.In addition, the homothermic purpose also is in order to let raw material film 6 in the time that the acquisition of thermostat temperature point is fully reacted and unified degree is reacted, to reach the purpose of good uniformity.The reason that slowly heats up also is the same; Because slowly intensification make to a certain extent raw material film 6 at one time in suffered temperature be identical basically; Level of response is also just the same basically like this, and the flaw that the molecular breakdown reorganization back of raw material film 6 occurs is just few.Select slow temperature rise rate at 500 ℃ to 700 ℃ temperature sections; Be because the decomposition of the molecule of raw material film 6 reorganization is very violent 500 ℃ to 700 ℃ the time; Wherein 550 ℃ to 650 ℃ is the most violent temperature section; Must be at this section by raw material film 6 homogeneous reactions, the flaw after the molecular breakdown reorganization is just few like this.
Present embodiment is warming up to 1200 ℃ with the speed of 3 ℃/min, constant temperature 30 minutes, naturally cooling then.
The adjustment of exerting pressure of raw material film 6 after the carbonization of the interval lamination of the weight application that 10. 9. step is obtained and the parts of mould.Open the bell of carbide furnace, replacement heatproof weight 5 above the loam cake 3 of the parts of the interval of weight application lamination and mould, and the raw material film 6 after the carbonization is applied certain pressure so that carry out graphitizing process.
Do not exert pressure during greying, the crystal structure of graphite poor continuity of graphite film then, physicals is also just poor.But the pressure of exerting pressure in the carbonization process must be less than the pressure of exerting pressure in the graphitizing process, because the reaction major part of raw material film 6 molecular breakdown, reorganization is at carbonization process, the graphitizing process molecular reaction is more light and slow.And in graphitizing process pressure little rise and to steep oneself-meeting manyly, crystal structure of graphite is flourishing (being the crystalline structure poor continuity) inadequately, physicalies such as heat conduction are also just poor, so the pressure of exerting pressure of graphitizing process wants big.The pressure range that graphitizing process is exerted pressure is 5.0 to 100g/cm
2, the pressure of exerting pressure in the graphitizing process can not be excessive, if pressure is higher than 100g/ cm
2, then too encourage the prosperity of the crystal structure of graphite of surface direction, it is very little to obtain the bubble degree, the very large hard graphite film of bubble area.Pressure is excessive so exert pressure, and the graphite film finished product can be more crisp, and snappiness is poor, and is fragile.
The adjustment of the quality of heatproof weight 5 is set to 6000g in this step.
After
waits for the carbide furnace naturally cooling, take out mfg. moulding die and obtain the finished product graphite film.
(embodiment 3)
The process of present embodiment is basic basic identical with embodiment 2, and its difference is: do not carry out step 6. in step before 7., promptly do not exert pressure to raw material film 6 in the carbonization process.The graphite film that makes has ripple, and carbonizing apparatus core warm area has light contamination.
(embodiment 4)
The process of present embodiment is basic identical with embodiment 2, and its difference is: after 9. step is accomplished, progressive suddenly 10., promptly in graphitizing process to raw material film 6 adjustment of exerting pressure.The graphite film quality that makes is soft partially, thermal diffusivity is poor slightly, and carbonizing apparatus core warm area has light contamination.
(embodiment 5)
The process of present embodiment is basic and embodiment 2 is basic identical; Its difference is: in step carbonization process 9.; Taked the operation of decompression when temperature is heated to 500 ℃ to 700 ℃, making carbide furnace equipment warm area internal gas pressure is little negative pressure-0.01KPa, after 700 ℃, keeps atmospheric pressure state.The graphite film that makes does not have the welding phenomenon, and carbonizing apparatus core warm area does not pollute.
(embodiment 6)
The process of present embodiment is basic and embodiment 2 is basic identical, and its difference is: step 6. in, the raw material film 6 in the mfg. moulding die is exerted pressure, the quality of the weight 5 of exerting pressure changes 3000g into;
In the step
, the quality of the weight 5 of exerting pressure is adjusted into 10000g.The graphite film that makes does not have the welding phenomenon, and carbonizing apparatus core warm area has light contamination.
(embodiment 7)
The process of present embodiment is basic basic identical with embodiment 2, and its difference is: step 1. in, the polyimide film of 50 microns of thickness, tensile strength 50MPa, diaxial orientation that adopts Liyang Huajing Electronic Material Co., Ltd.'s production is as raw material film 6;
In step carbonization process 9., when being heated to 500 ℃ to 700 ℃, temperature taked the operation of decompression, and making carbide furnace equipment warm area internal gas pressure is little negative pressure-0.01KPa, after 700 ℃, keeps atmospheric pressure state.The graphite film that makes does not have the welding phenomenon, and carbonizing apparatus core warm area has light contamination.
(embodiment 8)
The process of present embodiment is basic and embodiment 7 is basic identical, and its difference is: step 6. in, the raw material film 6 in the mfg. moulding die is exerted pressure, the quality of the weight 5 of exerting pressure changes 3000g into;
In the step
, the quality of the weight 5 of exerting pressure is adjusted into 10000g.The graphite film that makes does not have the welding phenomenon, and carbonizing apparatus core warm area does not produce pollution.
(comparative example)
Adopting the anti-LFA447 of the speeding thermal conductivity test appearance of Germany that the graphite film that makes is carried out thermal diffusivity measures.With there being data such as pollution-free to count table one in the atmospheric condition in the experimentation of embodiment 1 to 7, whether welding, thermal diffusivity, the carbide furnace.
Table one
The quality of rostone ink film, quality and technology have much relations, as exert pressure, quality that intensification etc. all influences finished product graphite, how design technology makes the graphite film of wanting will be designed according to demand separately.Technology of the present invention can be produced high-quality rostone ink film in batches, and this graphite film thermal diffusivity is good, the bending resistance folding endurance is strong, is suitable for solving small-sized electronic product components and parts heating problem.
Claims (10)
1. the mfg. moulding die of a flake graphite film is characterized in that: comprise base (1), column (2), loam cake (3), barrier sheet (4) and heatproof weight (5); Column (2) has 4;
Base (1) is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, and diameter is 20 to 50cm; The front, rear, left and right portion of base (1) respectively is provided with the through hole of 1 upward and downward; The adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base (1); And the axis of 4 through holes be positioned at the concentric cylindrical side of base (1) on, 4 through holes are equipped with IT;
4 root posts (2) are processed by graphite, and column (2) is cylindric, and the diameter of the through hole on its diameter and the base (1) is corresponding, and the bottom of every root post (2) is provided with the outside screw that the IT with the through hole of base (1) is complementary; 4 root posts (2) are screwed in corresponding 1 through hole of base (1) by its threaded portion, lower end respectively from top to bottom, thereby make 4 root posts (2) be fixed on the base (1), thereby obtain down membrane module;
Barrier sheet (4) has a rectangular shape, the imaginary foursquare length of side that its side ratio 4 root posts (2) are surrounded little by 0% to 0.2%; Barrier sheet (4) is processed by high temperature material; Barrier sheet (4) is horizontally set on when using in the space that base (1) and 4 root posts (2) surround;
Heatproof weight (5) is processed by high temperature material; The shape of heatproof weight (5) is consistent or slightly little with the shape of barrier sheet (4), and lower surface is smooth; Heatproof weight (5) is horizontally set on when using in the space that base (1) and 4 root posts (2) surround;
The shape of loam cake (3) and size are identical with base (1), and loam cake (3) is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, the equal diameters of diameter and base (1); The front, rear, left and right portion of loam cake (3) respectively is provided with the through hole of 1 upward and downward; The adjacent through-holes of 4 through holes is provided with respect to the central axis equal angles of base (1); And the axis of 4 through holes be positioned at the concentric cylindrical side of loam cake (3) on, 4 through holes of loam cake (3) are unthreaded hole; Pass a corresponding root post (2) respectively from top to bottom by its 4 through holes when loam cake (3) uses, and be fixed on the top of 4 root posts (2).
2. the mfg. moulding die of flake graphite film according to claim 1 is characterized in that: the preferred graphite flake of manufactured materials, rostone ink film or the natural stone ink film of barrier sheet (4), more preferably natural stone ink film;
The preferred carbon element class of the manufactured materials material of heatproof weight (5), more preferably graphite block; Heatproof weight (5) is bottom shape and barrier sheet (4) rectangular-shaped weight of a size.
3. the method for manufacture of a flake graphite film comprises the steps:
1. choose starting material, choose diaxial orientation, double refractive inde greater than 0.1, Young's modulus is greater than 400kgf/mm
2, the polyimide film of tensile strength more than 50Mpa be as the raw material film;
2. mfg. moulding die is set, and described mfg. moulding die adopts the mfg. moulding die of flake graphite film as claimed in claim 1;
3. the raw material film that 1. step is obtained is cut into the shape that is suitable for being placed in the mfg. moulding die that 2. step obtain; The foursquare shape size that is surrounded according to 4 root posts (2) of mfg. moulding die; The polyimide film that 1. step is obtained is cut into corresponding square shape and obtains raw material film (6), and the length of side of the foursquare barrier sheet of side ratio (4) of the raw material film (6) of the complete every square shape of cutting is little by 0.5% to 1%;
4. the raw material film (6) that 3. step is obtained and the spacing piece 4 of respective numbers are placed in the following membrane module that 2. step obtain with the mode of interval lamination; Be specially upper surface first raw material film of smooth placement (6) of the base (1) of the following membrane module that 2. obtains in step; Go up first barrier sheet of overlapping placement (4) at first raw material film (6) then; Second raw material film of overlapping again placement (6); Go up second barrier sheet of overlapping placement (4) at second raw material film (6) then; So superimposed until all raw material films (6) and barrier sheet (4) all are placed in the mfg. moulding die with space eclipsed mode, thus the subassembly of lamination and counterdie at interval obtained; The process of the above-mentioned overlapping placement in space abbreviates lamination process at interval as, and the overlapping placement in space then abbreviates lamination at interval as;
5. the raw material film (6) in the interval lamination that 4. step is obtained and the subassembly of counterdie is exerted pressure; Heatproof weight (5) is placed on the upper surface of the barrier sheet that is positioned at the top (4) of interval lamination that 4. step obtain and die assembly, thereby obtains the interval lamination of weight application and the parts of mould; The pressure range of exerting pressure is 3 to 10g/cm
2The interval lamination of the weight application that 6. 5. step is obtained and the parts of mould are put into the inner chamber of carbide furnace;
The inner chamber of the carbide furnace of the interval lamination of having put into weight application that 7. 6. obtains in step and the parts of mould, the inner chamber to carbide furnace vacuumizes earlier, charges into nitrogen or rare gas element again and forms inert environments;
8. under the inert environments that 7. step obtains; With the carbonization temperature of the raw material film (6) of the parts of the interval lamination of carbide furnace heat temperature raising to weight application and mould and begin carbonization; And under the highest carbonization temperature, be incubated 30 to 120 minutes and completion carbonization, naturally cooling then; The highest carbonization temperature that is provided with in the insulation is at 1000 ℃ to 1400 ℃;
The adjustment of exerting pressure of raw material film (6) after the carbonization of the interval lamination of the weight application that 9. 8. step is obtained and the parts of mould; Open the bell of carbide furnace; Replacement heatproof weight (5) above the parts of the interval of weight application lamination and mould, the pressure range of exerting pressure are 5.0 to 100g/cm
2
10. the carbide furnace that 9. step is obtained being provided with the parts of interval lamination and mould after adjustment is exerted pressure forms inert environments again; Earlier with vacuumizing in the stove, applying argon gas or helium to normal pressure, pressure-fired or little negative pressure then;
After
waits for the carbide furnace naturally cooling, take out mfg. moulding die and obtain the finished product graphite film.
4. the method for manufacture of flake graphite film according to claim 3 is characterized in that: step specified operational procedure 7. is: earlier carbide furnace is vacuumized, fill with rare gas element to normal pressure such as nitrogen or argon gas or pressure-fired, little negative pressure then; And then vacuumize again, fill with rare gas element to normal pressures such as nitrogen or argon gas or pressure-fired, little negative pressure again.
5. the method for manufacture of flake graphite film according to claim 4 is characterized in that: rare gas element nitrogen, the preferred little negative pressure of pressure condition.
6. the method for manufacture of flake graphite film according to claim 3 is characterized in that: step 1. in, the preferred all benzene type acid dianhydrides of polyimide raw material film and p-phenyl's diamines are as the prepared polyimide film of the polymer raw of polyimide.
7. the method for manufacture of flake graphite film according to claim 3; It is characterized in that: step 8. in; Temperature-rise period when described carbonization begins is included in 500 ℃ to 700 ℃ especially 550 ℃ to 650 ℃ the time, keeps slowly heating up with the speed below the 5 ℃/min.
8. the method for manufacture of flake graphite film according to claim 7; It is characterized in that: in step carbonization process 8.; In the time of 500 ℃ to 700 ℃, taked the operation of further decompression; The warm area air pressure that makes carbide furnace is little negative pressure-0.1KPa to-0.01KPa, after 700 ℃, keeps atmospheric pressure state.
9. the method for manufacture of flake graphite film according to claim 3; It is characterized in that: in the step
, heating schedule is warming up to top temperature in the graphitization process with the speed of 10 ℃ of-50 ℃/min in the described graphitization process.
10. according to the method for manufacture of the described flake graphite film of one of claim 3 to 9; It is characterized in that: after 4. step is accomplished, before 5. step carry out; Loam cake (3) is arranged on the subassembly that 4. step obtain at interval lamination and counterdie; Loam cake (3) is enclosed within respectively on the position, upper end of corresponding 1 root post (2) by its 4 through holes from top to bottom; Lower surface until loam cake (3) contacts with the upper surface that is in uppermost barrier sheet (4), thus make step 5. and heatproof weight (5) 9. be placed on the upper surface of loam cake (3).
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| CN103864068A (en) * | 2014-03-26 | 2014-06-18 | 苏州格优碳素新材料有限公司 | Method for preparing graphite film with high heat conductivity |
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| CN104291311A (en) * | 2012-12-28 | 2015-01-21 | 苏州斯迪克新材料科技股份有限公司 | Preparation process of graphite heat-conducting piece for electronic equipment |
| CN105683088B (en) * | 2013-11-28 | 2018-11-16 | 株式会社钟化 | The manufacturing method of graphite film |
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| CN104495795B (en) * | 2014-11-24 | 2017-03-08 | 云南云天化股份有限公司 | A kind of graphite flake and preparation method thereof |
| CN104495795A (en) * | 2014-11-24 | 2015-04-08 | 云南云天化股份有限公司 | Graphite flake and preparation method thereof |
| TWI548590B (en) * | 2015-02-13 | 2016-09-11 | Pin-Yu Ke | Artificial graphite sheet manufacturing method and its products |
| CN105000885A (en) * | 2015-06-30 | 2015-10-28 | 东莞市思泉实业有限公司 | Method for producing graphite film |
| WO2017183705A1 (en) * | 2016-04-22 | 2017-10-26 | 株式会社カネカ | Highly oriented graphite and method for producing highly oriented graphite |
| CN109911893A (en) * | 2018-12-04 | 2019-06-21 | 重庆云天化瀚恩新材料开发有限公司 | The preparation method of thermally conductive electrographite gasket |
| CN113292971A (en) * | 2021-06-01 | 2021-08-24 | 江西德思恩新材料有限公司 | Artificial graphite film with enhanced tensile strength for heat dissipation function and preparation method thereof |
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